CN104897824A - Gel chromatographic column and detection method for detecting poly brominated diphenyl ethers and metabolites thereof through GC-MC (gas chromatography and mass spectrography) - Google Patents
Gel chromatographic column and detection method for detecting poly brominated diphenyl ethers and metabolites thereof through GC-MC (gas chromatography and mass spectrography) Download PDFInfo
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Abstract
The invention provides a gel chromatographic column for detecting poly brominated diphenyl ethers and metabolites thereof through a GC-MC (gas chromatography and mass spectrography) method. The gel chromatographic column is prepared by the method comprising the following steps: weighing gel and a solvent, mixing the gel in the solvent, shaking to be uniform and swelling; taking a dry and clean chromatographic column, adding the solvent into the chromatographic column, discharging air bubbles between the lower part of a glass sand core filter plate and a piston, so that the space is filled with the solvent; and pouring the gel suspension liquid into the chromatographic column, and adding sea sand on the gel layer, thereby obtaining the gel chromatographic column. The preparation method of the gel chromatographic column is simple, complicated matrix effect can be overcome, and multiple impurities in the matrix containing organic pollutants can be separated, so that the multiple impurities can be effectively removed, and influences to follow-up detection for the organic pollutants are avoided. The invention further provides a method for detecting poly brominated diphenyl ethers and metabolites thereof based on the gel chromatographic column. The method has the advantages of simplicity in operation, good reproducibility, high sensitivity and high accuracy.
Description
Technical field
The present invention relates to the preparation method that a kind of gas chromatography mass spectrometry detects the gel chromatographic columns of PBDE and metabolin, and this gel chromatographic columns detects the detection method of PBDE and metabolin thereof, belongs to environment or technical field of food detection.
Background technology
At present, organic pollutant category in environment and food gets more and more, as PBDE and metabolin, it is the organic brominated flame retardant of a class halo (BFRs), due to good anti-flammability, it industrial circle by a large amount of uses in various commercial product, such as electric equipment products and textile.The PBBs ether product of business mainly comprises pentabromo-, eight bromines and decabromodiphenyl oxide.Due to their physicochemical property and biological accumulation feature, extensively distribute in physical environment as environmental persistence and high hydrophobicity result in this series products.Methoxyl polybrominated diphenyl ethers (MeO-PBDEs) is the class compound similar with PBBs ether structure, and they are considered to the compound of Prof. Du Yucang.Toxicologic study shows, this two compounds produces specific toxicological effect to the liver of human body, thyroid gland and reproductive organs and nervous system.And matrix residing for this kind of organic contaminant is usually very complicated, content is also very micro-, often in μ g/kg.At present, the detection method measuring PBDE and metabolin comparative maturity is GC-MS(gas chromatography-mass spectrography), but the accuracy of its result is largely limited by the impurity content of sample.If these impurity are not treated, then can produce larger interference to the testing result of follow-up organic contaminant, the result that impact detects.
Summary of the invention
The invention solves the deficiency in background technology, provide the gel chromatographic columns that a kind of gas chromatography mass spectrometry detects PBDE and metabolin thereof, this gel chromatography column preparation method is simple, effectively can overcome complicated matrix effect, can be separated containing the plurality of impurities in organic contaminant matrix, thus effectively remove plurality of impurities, avoid the interference that follow-up organic contaminant is detected.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind of gas chromatography mass spectrometry detects the gel chromatographic columns of PBDE and metabolin thereof, described gel chromatographic columns is adopted and is prepared with the following method: (1), take Aquapak A-440 and solvent, wherein every 1 gram of polystyrene correspondence measures 5 ~ 8 milliliters of solvents, described solvent is the mixed solution of cyclohexane and ethyl acetate, Aquapak A-440 is mixed in solvent, shake up, then carry out swelling, swelling time is greater than 24 hours, after swelling equilibrium, pour out supernatant and suspended particle impurity, for subsequent use;
(2) chromatographic column and a silica gel hose of a dried and clean, is got, silica gel hose is connected to the exit, lower end of chromatographic column, then in chromatographic column, add the solvent accounting for column volume 20 ~ 30%, leave standstill, until bubble-free is overflowed in glass core filter plate in chromatographic column, then open piston, extruding silica gel hose, discharge the bubble below glass core filter plate and between piston, make solvent be full of this segment space, then closure piston;
(3), Aquapak A-440 after swelling and solvent are poured in beaker, abundant stirring is until Aquapak A-440 suspends in a solvent uniformly, obtained gel suspension, then the top of gel suspension by chromatographic column is slowly poured in chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom is deposited into 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2 ~ 3mL/min, then continue to pour gel suspension into column volume 5/6 place, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the sea sand of 1/12 column volume is added on gel layer, pave, i.e. obtained described gel chromatographic columns.
Solvent cyclohexane described in step (1) and the volume ratio of ethyl acetate are 1:1.
The length-diameter ratio of the chromatographic column described in step (2) is 8 ~ 10:1.
The present invention additionally provides the method detecting PBDE and metabolin thereof based on above-mentioned gel chromatographic columns simultaneously, and the method has simple to operate, favorable reproducibility, the advantage that highly sensitive and accuracy is high.The method comprises the following steps: (1), mixed with the volume ratio of zeyssatite according to 1:8 ~ 10 by testing sample, wash-out is carried out according to the mixed solution of the volume ratio of 1:1 again with methylene chloride and normal hexane, collect and concentrate testing sample eluent, obtained concentrate A;
(2) in concentrate A, add interior mark carbon 13 mark interior mark PBDEs 28,47,99,100,154,153 and 183, concentration is 100ng/mL, and BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68,5 '-MeO-BDE99, the mixed standard solution of 5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103, concentration is 100ng/mL; Above material to be added in concentrate and to mix, then concentrate being injected in chromatographic column, until the liquid level of concentrate is concordant with extra large sand face;
(3), the solvent of 1.2 ~ 1.4 times of column volumes is adopted to carry out wash-out, elution flow rate is 1.00 ~ 1.50mL/min, discard the eluent of front 50 ~ 60% column volumes, collect the eluent of remainder in evaporative flask, follow-up blowing through rotary evaporation and nitrogen is concentrated into 0.9 ~ 1.1mL, obtained concentrate B, detects for GC-MS;
(4), by concentrate B inject GC-MS, adopt Elite-5MS capillary chromatographic column, sampling volume is 2.0 ~ 3.0 μ L, not shunt mode sample introduction, and using helium as carrier gas, flow rate of carrier gas is 0.8 ~ 1.2mL/min.Injector temperature is 270 ~ 280 DEG C, bushing pipe adopts deactivation bushing pipe, transmission line temperature is 315 DEG C ~ 325 DEG C, ion source temperature 245 DEG C ~ 255 DEG C, the EI of 70ev is adopted to ionize mode, scan mode is SIM, and column oven temperature programme condition is: 95 DEG C ~ 105 DEG C keep 0.8 ~ 1.2min → 195 DEG C ~ 205 DEG C, programming rate to be 18 DEG C/min ~ 22 DEG C/min; 195 DEG C ~ 205 DEG C → 275 DEG C ~ 285 DEG C, programming rate is 2.4 DEG C/min ~ 2.6 DEG C/min; 275 DEG C ~ 285 DEG C → 315 DEG C ~ 325 DEG C, programming rate is 4.5 DEG C/min ~ 5.5 DEG C/min, 315 DEG C ~ 325 DEG C keep 9 ~ 11min;
(5), adopt Isotope internal standard dilution standard measure, namely be horizontal ordinate with testing concentration, determinand peak area and corresponding isotopic peak area ratio are ordinate, obtain working curve, thus BDE17 in testing sample in calculating, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47, 6-MeO-BDE47, 4 '-MeO-BDE49, 2 '-MeO-BDE68, 5 '-MeO-BDE99, 5 '-MeO-BDE100, the content of 4 '-MeO-BDE101 and 4 '-MeO-BDE103.
It is a kind of very effective disposal route that gel is separated, when in matrix, the potpourri of different molecular size flows through gel chromatography column, the molecule larger than gel mesh can not enter the reticulate texture in microgel particle, and by outside exclusion Gel particulate, flow downward along with the hole of solvent between microgel particle and flow out at first outside post; Inside and outside the molecular energy less than mesh microgel particle of freely coming in and going out in various degree is cancellated, hold-up time is in the chromatography column longer, be separated due to the distance difference of the molecule institute warp of different size like this, macromolecular substances by first wash-out out, as protein, small-molecule substance by rear wash-out out, as PBDE and metabolin.Therefore, sample, after gel chromatography separation purification, can remove most of impurity, has facilitation to the accuracy measuring PBDE and metabolin.Then sample solution is concentrated, measure for GC-MS.
First good separating effect to be expected, gel must carry out swelling treatment, after swelling, gel volume expands, among solvent penetration to gel, the reticulate texture of microgel particle could fully stretch, and such macromolecular substances could by exclusion, small-molecule substance can freely be come in and gone out, thus reaches good isolation of purified effect.
Secondly dress post must be wanted evenly, smooth, can not have bubble.Bubble derives among the space below glass core filter plate usually, adopts the mode of silica gel hose exhaust bubble, solvent can be made to be full of dead volume below glass core filter plate and between piston, thus suppress the generation of bubble.In dress post process, the homogeneity of gel is also extremely important, and the pine that namely can not cross of gel dress can not tension, if the too pine of dress, in chromatography process, gel layer height can decline, the tension of dress, then wash-out resistance is too large, extends analysis time.And adopting dress column method of the present invention, the tightness of gel is just right.
The present invention employs extra large sand at the top layer of chromatographic column, sea sand principal ingredient is silicon dioxide, stable in properties, do not react with other compounds, gel compacting can flatten by extra large sand in the filling process, and then in loading and elution process, due to extra large sand buffer action, gel can not be kicked up because of impulsive force.
The present invention's agents useful for same in purification process is environmentally friendly reagent, cyclohexane and ethyl acetate little compared with methylene chloride toxicity, also little to the pollution of environment.The present invention can avoid the dichloromethane solvent that operating personnel's contact toxicity is stronger, reduces the harmfulness to human body and environment.
The present invention is also optimized chromatography of gases Mass Spectrometry Conditions, injector temperature is set to 270 ~ 280 DEG C, ensure that the gasification cmpletely of institute's analysis of compounds, bushing pipe adopts deactivation bushing pipe, the active site adsorption sample component on injection port bushing pipe can be avoided and cause occurring tailed peak, especially for some high boiling substances in PBBs ether compound.Transmission line temperature is set to 315 DEG C ~ 325 DEG C, ensure that determinand enters the process of mass detector from gas chromatography and condensation effect does not occur.
The present invention is analytical approach, Isotope internal standard dilution method has been selected to come quantitatively, this method quantitatively on more accurate science, the error that the interference (ion suppress and so on) due to sample mesostroma causes can be got rid of, before sample purification, add interior mark compound simultaneously can also investigate damaed cordition to target compound in whole experimentation.
Compared with prior art, its beneficial effect and advantage are in the present invention:
The gelling performance prepared in the present invention is superior, and in the method, the padding of gel describes specifically careful, with strong points, thus strengthens operability.Therefore, gel purification chromatographic column prepared by the method can overcome complicated matrix effect, can remove containing the plurality of impurities in polybrominated biphenyl and metabolin matrix thereof, eliminates and detects to follow-up PBBs and metabolin thereof the interference produced; Follow-up detection method give also the suitableeest parameter of instrument, makes the result of analysis more accurately and reliably.The more important thing is, solidifying purification chromatographic column prepared by the method is simple to operate, the results showed, use the method detect the organic contaminants such as PBBs compounds have highly sensitive, accuracy is high, favorable reproducibility and the high advantage of the recovery.
Embodiment
Below in conjunction with specific embodiment, detailed specific description is done to the present invention, but protection scope of the present invention is not limited to following examples.
PBDE and the gel chromatographic columns of metabolin and the feasibility of detection method thereof and superiority is detected for checking gas chromatography mass spectrometry provided by the invention, present inventor specially adds mixed standard solution and the inner mark solution of PBDE and metabolin thereof in dairy products, adopted by the dairy products of mark-on solution the preparation of gel purification chromatographic column provided by the invention to be separated with fill method, detect according to instrument parameter provided by the invention.Measure the PBDE of dairy products after gel purification chromatographic column is separated and the content of metabolin thereof, according to the difference of the result concentration detected and known organic concentration, the feasibility detect separation and the instrument of gel purification chromatographic column prepared by the method and superiority are assessed.
Embodiment 1
Get 100g Aquapak A-440, be immersed in the cyclohexane of 500mL: in ethyl acetate (1:1), shake up, then carry out swelling, swelling time is one day, after swelling equilibrium, pours out supernatant and suspended particle impurity, for subsequent use.Get a clean chromatographic column (ID:2.5cm × L:20cm), add the cyclohexane of about 5cm: ethyl acetate (1:1), leave standstill, until bubble-free is overflowed in glass core filter plate in chromatographic column, then open piston, extruding silica gel hose, discharge the bubble below glass core filter plate and between piston, solvent is made to be full of this segment space, then closure piston.Aquapak A-440 after swelling and solvent are poured in beaker, abundant stirring is until Aquapak A-440 suspends in a solvent uniformly, obtained gel suspension, then the top of gel suspension by chromatographic column is slowly poured in chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom is deposited into 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2 ~ 3mL/min, then continue to pour gel suspension into 17cm place, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the sea sand that 1.6cm is high is added on gel layer, pave, i.e. obtained described gel chromatographic columns.
Take the milk powder that 2g processed in advance, mix with the zeyssatite of 16g, the methylene chloride with 150mL: normal hexane (1:1) carries out wash-out extraction, collect extract, be concentrated into 1mL, obtained concentrate A.In concentrate A, add interior mark carbon 13 mark interior mark PBDEs 28,47,99,100,154,153 and 183, concentration is 100ng/mL, and BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68,5 '-MeO-BDE99, the mixed standard solution of 5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103, concentration is 100ng/mL; Above material to be added in concentrate and to mix, then concentrate being injected in chromatographic column, until the liquid level of concentrate is concordant with extra large sand face.
Carry out wash-out with 120mL solvent (cyclohexane: ethyl acetate 1:1), discard front 60mL eluent, elution flow rate is 1mL/min.60mL eluent after collecting, eluent is evaporated to 1.0mL, and obtained concentrate B, detects for GC-MS.
Concentrate B is injected GC-MS, and adopt Elite-5MS capillary chromatographic column, sampling volume is 2.0 μ L.Not shunt mode sample introduction.Helium is as carrier gas.Flow rate of carrier gas is 0.8mL/min.Injector temperature is 270 DEG C, and bushing pipe adopts deactivation bushing pipe.Transmission line temperature is 315 DEG C, and ion source temperature is 245 DEG C.Adopt the EI of 70ev to ionize mode, scan mode is SIM.
Column oven temperature programme condition is: 95 DEG C (keeping 0.8min) → 195 DEG C, 18 DEG C/min; 195 DEG C → 275 DEG C, 2.4 DEG C/min; 275 DEG C → 315 DEG C, 4.5 DEG C/min (keeping 9min).
By Isotope internal standard dilution method, sample is carried out quantitatively, and calculate the recovery, record BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68, the recovery of 5 '-MeO-BDE99,5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103 is 70% ~ 110%.
The result of the above-mentioned recovery meets the related request in european union directive (European Union document 2002/657/EC).Namely during P < 1 μ g/L, the recovery need in 50% ~ 120% scope, and P refers to the concentration of determinand.
Embodiment 2
Get 100g Aquapak A-440, be immersed in the cyclohexane of 800mL: in ethyl acetate (1:1), shake up, then carry out swelling, swelling time is one day, after swelling equilibrium, pours out supernatant and suspended particle impurity, for subsequent use.Get a clean chromatographic column (ID:3cm × L:30cm), add the cyclohexane of about 7.5cm: ethyl acetate (1:1), leave standstill, until bubble-free is overflowed in glass core filter plate in chromatographic column, then open piston, extruding silica gel hose, discharge the bubble below glass core filter plate and between piston, solvent is made to be full of this segment space, then closure piston.Aquapak A-440 after swelling and solvent are poured in beaker, abundant stirring is until Aquapak A-440 suspends in a solvent uniformly, obtained gel suspension, then the top of gel suspension by chromatographic column is slowly poured in chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom is deposited into 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2 ~ 3mL/min, then continue to pour gel suspension into 25cm At The Height, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the sea sand that 2.5cm is high is added on gel layer, pave, i.e. obtained described gel chromatographic columns.
Take the milk powder that 3g processed in advance, mix with the zeyssatite of 30g, the methylene chloride with 250mL: normal hexane (1:1) carries out wash-out extraction, collect extract, be concentrated into 1mL, obtained concentrate A.In concentrate A, add interior mark carbon 13 mark interior mark PBDEs 28,47,99,100,154,153 and 183, concentration is 100ng/mL, and BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68,5 '-MeO-BDE99, the mixed standard solution of 5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103, concentration is 100ng/mL; Above material to be added in concentrate and to mix, then concentrate being injected in chromatographic column, until the liquid level of concentrate is concordant with extra large sand face.
Carry out wash-out with 250mL solvent (cyclohexane: ethyl acetate 1:1), discard front 150mL eluent, elution flow rate is 1.5mL/min.100mL eluent after collecting, eluent is evaporated to 1.0mL, and obtained concentrate B, detects for GC-MS.
Concentrate B is injected GC-MS, and adopt Elite-5MS capillary chromatographic column, sampling volume is 3.0 μ L.Not shunt mode sample introduction.Helium is as carrier gas.Flow rate of carrier gas is 1.2mL/min.Injector temperature is 280 DEG C, and bushing pipe adopts deactivation bushing pipe.Transmission line temperature is 385 DEG C, and ion source temperature is 255 DEG C.Adopt the EI of 70ev to ionize mode, scan mode is SIM.
Column oven temperature programme condition is: 105 DEG C (keeping 1.2min) → 205 DEG C, 2.2 DEG C/min; 205 DEG C → 285 DEG C, 2.6 DEG C/min; 285 DEG C → 325 DEG C, 5.5 DEG C/min (keeping 11min).
By Isotope internal standard dilution method, sample is carried out quantitatively, and calculate the recovery, record BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68, the recovery of 5 '-MeO-BDE99,5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103 is 70% ~ 110%.
The result of the above-mentioned recovery meets the related request in european union directive (European Union document 2002/657/EC).Namely during P < 1 μ g/L, the recovery need in 50% ~ 120% scope, and P refers to the concentration of determinand.
Claims (4)
1. the gel chromatographic columns of a gas chromatography mass spectrometry detection PBDE and metabolin thereof, it is characterized in that described gel chromatographic columns is adopted to prepare with the following method: (1), take Aquapak A-440 and solvent, wherein every 1 gram of polystyrene correspondence measures 5 ~ 8 milliliters of solvents, described solvent is the mixed solution of cyclohexane and ethyl acetate, Aquapak A-440 is mixed in solvent, shake up, then carry out swelling, swelling time is greater than 24 hours, after swelling equilibrium, pour out supernatant and suspended particle impurity, for subsequent use;
(2) chromatographic column and a silica gel hose of a dried and clean, is got, silica gel hose is connected to the exit, lower end of chromatographic column, then in chromatographic column, add the solvent accounting for column volume 20 ~ 30%, leave standstill, until bubble-free is overflowed in glass core filter plate in chromatographic column, then open piston, extruding silica gel hose, discharge the bubble below glass core filter plate and between piston, make solvent be full of this segment space, then closure piston;
(3), Aquapak A-440 after swelling and solvent are poured in beaker, abundant stirring is until Aquapak A-440 suspends in a solvent uniformly, obtained gel suspension, then gel suspension is poured in chromatographic column by the top of chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom is deposited into 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2 ~ 3mL/min, then continue to pour gel suspension into column volume 5/6 place, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the sea sand of 1/12 column volume is added on gel layer, pave, i.e. obtained described gel chromatographic columns.
2. gel chromatographic columns according to claim 1, is characterized in that: the solvent cyclohexane described in step (1) and the volume ratio of ethyl acetate are 1:1.
3. gel chromatographic columns according to claim 1, is characterized in that: the length-diameter ratio of the chromatographic column described in step (2) is 8 ~ 10:1.
4. one kind is detected the method for PBDE and metabolin thereof based on gel chromatographic columns according to claim 1, it is characterized in that comprising the following steps: (1), testing sample is mixed with the volume ratio of zeyssatite according to 1:8 ~ 10, wash-out is carried out according to the mixed solution of the volume ratio of 1:1 again with methylene chloride and normal hexane, collect and concentrate testing sample eluent, obtained concentrate A;
(2) in concentrate A, add interior mark carbon 13 mark interior mark PBDEs 28,47,99,100,154,153 and 183, concentration is 100ng/mL, and BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68,5 '-MeO-BDE99, the mixed standard solution of 5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103, concentration is 100ng/mL; Above material to be added in concentrate and to mix, then concentrate being injected in chromatographic column, until the liquid level of concentrate is concordant with extra large sand face;
(3), the solvent of 1.2 ~ 1.4 times of column volumes is adopted to carry out wash-out, elution flow rate is 1.00 ~ 1.50mL/min, discard the eluent of front 50 ~ 60% column volumes, collect the eluent of remainder in evaporative flask, follow-up blowing through rotary evaporation and nitrogen is concentrated into 0.9 ~ 1.1mL, obtained concentrate B, detects for GC-MS;
(4), concentrate B is injected GC-MS, adopt Elite-5MS capillary chromatographic column, sampling volume is 2.0 ~ 3.0 μ L, not shunt mode sample introduction, using helium as carrier gas, flow rate of carrier gas is 0.8 ~ 1.2mL/min, injector temperature is 270 ~ 280 DEG C, bushing pipe adopts deactivation bushing pipe, transmission line temperature is 315 DEG C ~ 325 DEG C, ion source temperature 245 DEG C ~ 255 DEG C, the EI of 70ev is adopted to ionize mode, scan mode is SIM, column oven temperature programme condition is: 95 DEG C ~ 105 DEG C keep 0.8 ~ 1.2min → 195 DEG C ~ 205 DEG C, programming rate is 18 DEG C/min ~ 22 DEG C/min, 195 DEG C ~ 205 DEG C → 275 DEG C ~ 285 DEG C, programming rate is 2.4 DEG C/min ~ 2.6 DEG C/min, 275 DEG C ~ 285 DEG C → 315 DEG C ~ 325 DEG C, programming rate is 4.5 DEG C/min ~ 5.5 DEG C/min, 315 DEG C ~ 325 DEG C keep 9 ~ 11min,
(5), adopt Isotope internal standard dilution standard measure, namely be horizontal ordinate with testing concentration, determinand peak area and corresponding isotopic peak area ratio are ordinate, obtain working curve, thus BDE17 in testing sample in calculating, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolin 5-MeO-BDE47, 6-MeO-BDE47, 4 '-MeO-BDE49, 2 '-MeO-BDE68, 5 '-MeO-BDE99, 5 '-MeO-BDE100, the content of 4 '-MeO-BDE101 and 4 '-MeO-BDE103.
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| CN105158379A (en) * | 2015-08-19 | 2015-12-16 | 中国检验认证集团湖北有限公司 | Gel chromatographic column for detecting PBDEs (poly brominated diphenyl ethers) and hydroxyl metabolites of PBDEs through HPLC-MS as well as detection method of gel chromatographic column |
| CN106248815A (en) * | 2016-07-11 | 2016-12-21 | 环境保护部华南环境科学研究所 | The monomer stabilization carbon isotope analysis method of PBDE in fish body |
| CN110068634A (en) * | 2019-06-06 | 2019-07-30 | 华东师范大学 | The detection method of 12 kinds of polybrominated diphenyl ethers in a kind of soil |
| CN113933408A (en) * | 2021-09-09 | 2022-01-14 | 国家粮食和物资储备局科学研究院 | Analysis method of polybrominated diphenyl ethers in grains |
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| CN113933408A (en) * | 2021-09-09 | 2022-01-14 | 国家粮食和物资储备局科学研究院 | Analysis method of polybrominated diphenyl ethers in grains |
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